Dyestuffs of the dibenzanthrone series



: uary '11, 1928.

ma mas {or 1 iTilE "DIBENZANTHRONE seams r Lewis "Max AlbertKunz,Mani1heim, and Karl Koeberle,

- Ludwigshafemo1i=tl1e-Rliine,' Germany, assigna ors to General AnilineWorks, Inc, New York, N. Y.', at corporation of Delaware N0 Drawing;Application-January 22, 1032, Se- 1 v -rial'l \To.-58 8,2 3-1. InGermany June 9, 1927 teams. (01. gen-451) The present relates to'ne'wdyestufis of the dibenzanthrone 'se'riesa'rid process of pro-- ducingsame and is a continuation-in-part of our copending applicationser. lIo. 246,078,.filed Jan- We have found that valuable vat dyestufl fsfare'obtained by condensing a dibenzanthrorie' which term is meant to includea1so' isodiben'zanthrones, containing "from 2 to fi haloge'n atoms, withan aminoanthraquinone p1,..a, derivativethereof. The condensation isbrought, about by heating the components together iuthelpresh'cb ofloop: per or a compoundthereof and an acid-binding agent. Coppercompounds which 'mayfbelused, are, for example, coppersalts, such ascarbonate,

acetate, oxalate; sulphate, nitrate and halides,

cupric and .cuprous oxides; As acid-binding agents may be mentioned thealkali and alkaline earth metal salts of weak'acids, forexamplecarbonic, acetic, oxalic .acid, secondary and. tertiaryphosphates (if alkali metalsjcalciumapd. magnesiumoxides,dimethy1ani1ine, quindline and the like. The condensation is;preferably carried out in inert organic solventsfin particulararomaticso1veiitsdf hig h boiling point, such as-nitro derivatives ofbenzene and its h6mologues'fhaphthalene, quinolihe anddimethylamline.Amino anthraquin'on'e's whicli may be used for the prep ar'ation ofthe-dyestulis, are for-example, mono-j and poly aniino derivatives-of"anthraquinone it; self, its fho'molo'gue's "and-"their substitutionprod ucts and-derivatives'in which "the tvro ket'o groups are unaltered;r r example-s'uch asare substituted by "simple substitue'nts'such ashydroxy, alkoxy, cyano, alkylamino, aryl-amino including anthra'quinonyl amino and. aldehydegrOups or by an attached nuclear system asin the case of amino derivatives of anthrimidecarbazoles (diphthaloylcarbazole), anthraquinone-acridones, -thi oxanthones,--oxazoles and-imidazoles. V .Y The new dyestufis are obtained in. very goodyieldsaccording to the processwdescribed. and mostly in a pure state. Ifnecessary, they may be purified by recrystallization from organicsolvents,=b y reprecipitation irom their solutions in concentratedsulphuric acid, or by treatingtheir aqueous pastes with an oxidizingagent, for example an alkali metal hypochlorite solution. The dyestuffsform dark powders dissolving in concentrated sulphuric acid to giveviolet or green solutions and dye the vegetable fiber usually violet,dark blue to olive and grey shades from usu ually blue to brown violetvats. i

The following examples will further illustrate the nature of thisinvention but the invention is not limited to these examples. The partsare by weight- Example! 12.5 parts of dibromodibenzanthrone (prepared bybromihating. dibenzanthrone in chlorosulphonic acid inthe presence ofsulphur) are boiled .for'flS hours, while stirring, in amixture of 250partspf nitrobenzene', 2.5 parts of copper carbonate; 10 parts of sodiumcarbonate and 10 part's'of l-aminoanthraquinone; the" reaction productis filtered off by suction, while hot, and is then boiled with water.and dilute acid for removing inorgan'ic. constituents, and dried afterfiltration. V

IThe black powder obtained gives a blue solution with concentratedsulphuric acid and grey to blue-"- black dyeings of excellent fastnesson cotton from ablue vat.

' Example? 11 parts "of .dichloro-dibenzanthrone (obtainable bychlorinating dibenzanthrone in"ch.lo'rosulphonic acid inlthe presence ofsulphur) are suspended in parts of nitrobenzeneyS parts of sodiumacetate, 1.5 parts of copper carbonate and 5 parts of1.4-amino-methoxyanthraquinone are added and the mixture is boiled forZOhours while stirring. The reaction product is filtered off by suctionwhile hot and worked up as'described in Example 1. The black powder soobtainecl dyes cottonfrom a green-blue vat blue grey to blue-blackshades of excellent fastness and dissolves to a blue solution inconcentrated sulphuric acid; 7

, Example 3- '62 parts of dibromo isodibenzanthrone obtain: able by brominating' isodibenzanthrone in nitric: benzene are boiled for'15 hourswhile stirring in amixture of 1000parts of nitrobenzene, 30vpart's ofsodiumacetate, 2parts of copper carbonate o partsof cupric oxide and 50parts of 1.4amino-.

methoxyanthraquinone; The reaotionproduct is filtered. off by suctionwhile hot and. worked up gives blue solutions in concentrated ,su1phuric'acid. V

Example 4 63 parts of penta-chlorodibenzanthrone (obtainable bychlorinating dibe'nzanthrone in nitrobenzene) are heated to boiling forfrom 10 to 15 hours, while stirring, in 1000 parts of naphthalenequinone equivalent amounts of lA-diaminoan-f thraquinone,1-amino-5benzoylaininoanthra quinone, 1-amino-8benzoylaminoanthraquinone, 1 amino-5-benzoylamino-8 methoxyanthraquinoneor amino-acylaminoanthraquinones substi tuted in the acid radical may beused for the condensation, whereby products are obtained which,generally speaking, dye cotton grey to dark blue shades. I V

The condensation product of penta-chloroisodibenzanthrone (obtainable byheating isodie benzanthrone in trichlorobenzene with ferric chloride)and a-aminoanthraquinone yield likewise grey shades on cotton. I

In an analogous manner from di-','triand tetra-halogendibenzanthrones bycondensation withfrom 2 to 4 equivalent amounts ofa-arninobenzoylaminoanthraquinone products are obtained dyeing cottonfrom violet-brown to blue vatsviolet, dark blue to grey shades.

' Erample 5 j 62 parts of dibromoisodibenzanthrone areheated to boiling,while stirring, in 500 parts of nitrobenzene with 46 parts ofB-aminoanthraquinone, after the addition of 25 parts of sodium acetate'a'nd '7 parts of copper carbonate until the reac-.

tion product is practically free" from bromine. Thereaction mixture isthen allowed to cool and worked up in the usual manner. tion product.thus obtained is a blue-black powder dissolving in concentratedsulphuric acid to 'u-aminoanthraquinone.

give an olive-green solution and dyes cotton strong navy-blue shadesfrom a blue vat.-

Strong violet shades of very good fastness are obtained on cotton by thecondensation product of -l.molecular proportion of6,6-dichloroisodibenzanthrone and 2: molecular proportions of Example 6V partsof tribromodibenzanthrone are heated to boiling, while stirring,in 1000 parts of nitrobenzene after the addition of '75 parts'ofl-aminoanthraquinone-2-aldehyde, 50 parts of calcined soda and '5 partsof copper oxide until the reaction 'product is practically free .frombromine. 'Ihereaction mixture is then allowed to cool, and worked up asusual. The reaction productjob tained in the form of ablue-black'powder'dissolves in concentrated sulphuricacidto givea violetsolution and dyes cotton froma violet-grey vatrstrong grey shades ofvery good fastness. v

'A product having similar properties is obtained by replacing the partsof l-aminoanthraqui'none-2-aldehyde by 69 partsof aeaminoanthraquinone.

The condensa- Example 7 v 62 parts of -dibromodibenzanthrorie areiheatedto boiling in 1000 parts of nitrobenzene with 84 parts of4-amino-3,5-dichloroanthraquinone 2,1-(N)--benz acridone afterthe=additi0n;= of 50 parts of sodium acetate. and 75. parts" of f copperoxide. until the reaction productis practically free 1 N from bromide.After cooling the reaction mixture is worked up in the usual manner. Thecondensation productthus obtained is a green-black pow der dissolving inconcentrated sulphuric acid to givea violet solution and dyesthe'rveget'able fiber j strong olive shades from a violet vat.

The reaction product obtained in an analogous manner from dibromoordichloroisodibenzanthrone dyes dark .blue shades.

By condensation of '1 molecular proportionof Idichlorodibromodibenzanthrone with 4 molecular proportions of4-amino-5'-benzoylamino -8-methoxy-Ll' dianthrimidecarbazole areaction-prod not is obtained dyeing irorn grey to black shades l IEaizimple 8-5;. 78 parts "of tetrabrornoisodib enzarithrone areheated-to boiling, while stirring, in 1000 parts of; nitrobenzen'e with200 parts of 4"-an'iinoj-j1'-B2 1 benzanthrone arninoanthraquinone"(obtainable by condensation of Bzl-ebromobenzanthrone;with

1-amino-4-benzoylaminoanthraquinonei insing i the "condensation productwith' jcaustici potash mixture is then wo'rked'up. in the usual manner.

Theco'nden'sation product thus obtained is ablue black powder anddyes'cotton a V very fast dark blue shades from a blue wit. 1 What weclaim is:

formula: I I .R N, R1; e v I I wherein R. stands fora dibenzanthroneradical, ,RV-stands for a radical of an anthraquinonea tv tached inits-alpha position to, the nitrogenatomv and containing a benzoylamino.group andxis any member from 2" to 5 which dyestuffs dissolveinconcentrated sulphuric acid to giveblue gto violet or.- green solutionsand usually .dye the vegetable fiber 'from blue -to -brown- -,violetvatsviolet, dark blue toolive and grey shades.

2. .The vat :dyestufi correspondingto the-for;

which dyestufi dissolves in concentrated Sulphuric acid to give avioletsolution and dyes cotton mm;

a brown-violet vat grey shadesf -MAX ALBERT KUNZZ:

